CN110655642B - Carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material as well as preparation method and application thereof - Google Patents
Carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN110655642B CN110655642B CN201910993619.XA CN201910993619A CN110655642B CN 110655642 B CN110655642 B CN 110655642B CN 201910993619 A CN201910993619 A CN 201910993619A CN 110655642 B CN110655642 B CN 110655642B
- Authority
- CN
- China
- Prior art keywords
- carbazolyl
- phosphonium salt
- quaternary phosphonium
- microporous material
- polymer microporous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 title claims abstract description 106
- 150000004714 phosphonium salts Chemical group 0.000 title claims abstract description 78
- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 239000012229 microporous material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 150000004032 porphyrins Chemical class 0.000 claims description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 28
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 238000010898 silica gel chromatography Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- YMJWXVPIBWNCQT-UHFFFAOYSA-N 1-bromopropoxybenzene Chemical compound CCC(Br)OC1=CC=CC=C1 YMJWXVPIBWNCQT-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 44
- 229910002092 carbon dioxide Inorganic materials 0.000 description 22
- 239000001569 carbon dioxide Substances 0.000 description 22
- 239000011148 porous material Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000005676 cyclic carbonates Chemical class 0.000 description 6
- 150000002118 epoxides Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000013317 conjugated microporous polymer Substances 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000013310 covalent-organic framework Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- FBTOLQFRGURPJH-UHFFFAOYSA-N 1-phenyl-9h-carbazole Chemical class C1=CC=CC=C1C1=CC=CC2=C1NC1=CC=CC=C12 FBTOLQFRGURPJH-UHFFFAOYSA-N 0.000 description 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 238000001875 carbon-13 cross-polarisation magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical class N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/147—Side-chains with other heteroatoms in the side-chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/43—Chemical oxidative coupling reactions, e.g. with FeCl3
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a preparation method of a quaternary phosphonium salt and metalloporphyrin polymer microporous material containing polycarbazolyl, which comprises the steps of stirring and mixing metalloporphyrin containing carbazolyl and a quaternary phosphonium salt monomer containing carbazolyl in an inert atmosphere in the presence of an oxidant and an organic solvent, and carrying out oxidation reaction to obtain the quaternary phosphonium salt and metalloporphyrin polymer microporous material containing polycarbazolyl.
Description
Technical Field
The invention belongs to the field of organic porous polymer materials, and particularly relates to a carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material, and a preparation method and application thereof.
Background
Carbon dioxide is the most important greenhouse gas on the earth, the reduction of the emission of carbon dioxide is an important strategic subject of governments and scientific communities of all countries at present, and carbon dioxide is also a carbon resource which is most widely distributed and most abundant in reserves on the earth, so that the carbon dioxide can be converted into chemical products beneficial to human beings as a carbon resource while the emission of the carbon dioxide is reduced, and therefore, the research on the fixation and chemical conversion of the carbon dioxide has important significance. The conversion of carbon dioxide is realized in many ways, mainly including catalytic activation, electrochemistry, photochemical reduction and the like, and the utilization of carbon dioxide by chemical conversion is the most convenient and potential approach for industrialization from the viewpoint of feasibility. However, since carbon dioxide has high thermodynamic stability and low reactivity, it is difficult to react in a general environment, and thus heterogeneous catalysts, such as metal oxides, porous polymers, and metal complexes, which are convenient to separate and recover, have been developed.
The porous polymer material has rich porosity, mainly comprises light elements such as carbon, hydrogen, oxygen, nitrogen, boron and the like, and has strong research interest due to the advantages of rich skeleton composition, strong modification, good stability, high specific surface area, adjustable pore channel structure and the like. Porous polymer materials are mainly divided into covalent organic framework materials (COFs), Conjugated Microporous Polymers (CMPs) and metal organic framework Materials (MOFs); the covalent organic framework material is a novel porous material of organic units skillfully connected by stable covalent bonds, has higher porosity and crystallinity, realizes complex organic construction units by covalent bonding among atoms, and is a regular and orderly-arranged porous structure; the conjugated microporous polymer is a high molecular porous material with a pi conjugated structure, the conjugated structure is caused by that two p orbitals (or d orbitals) and a middle sigma bond are overlapped to form an alternate single-double structure, S bonds which freely rotate between the building units enable the conjugated microporous polymer to be an amorphous structure, but the size of the aperture of the polymer and the size of the specific surface area can be regulated and controlled by changing rigid connecting molecules; the metal organic framework material has the advantages of softness, light weight, diversity of spatial structure, large specific surface area, strong hydrogen storage capacity and the like.
Porphyrin is a general name of homologues and derivatives of porphin with substituent groups on the outer ring, is a special macrocyclic conjugated aromatic system, and can be applied to the fields of organic reaction catalysts, solid adsorbents, optical storage devices, supramolecular chemistry and the like due to the specific pi conjugated system and coordination function. Currently, there are two main types of methods for synthesizing porphyrin-containing porous polymers: (1) forming a porphyrin ring with a functional group by using micromolecules with the functional group, and then preparing a porous polymer by selecting a proper reaction; (2) modifying the functional group of the formed porphyrin mother nucleus to prepare the porous polymer. However, these two methods have problems that the preparation of porphyrin ring molecules is easy but the yield is not high, most of the polymers synthesized in the later period need noble metal catalysts and the cost is high, which is not favorable for large-scale industrial production, thereby limiting the practical application.
In recent years, carbazole is an important nitrogen-containing heterocyclic compound, which is relatively stable to heat, acid and alkali, and has a rigid main chain and a conjugated electron-rich system, so that a permanent porous material can be formed, the interaction between an adsorbate and an adsorbent can be enhanced, and the nitrogen-containing structure can greatly improve the adsorption capacity of the carbazole on carbon dioxide acid gas, but the adsorption capacity of a single unmodified carbazole porous material doped with any element is limited, so that the carbazole porous material cannot meet the requirement of industrial adsorption conversion on carbon dioxide.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material, a preparation method and application thereof, and the microporous material prepared by the preparation method can be used as a bifunctional catalyst for promoting carbon dioxide and epoxide to generate cyclic carbonate and has potential application in aspects of carbon dioxide storage, molecular isolation, heterogeneous catalysis, chemical or biological sensors and the like.
The technical scheme of the invention is as follows:
the invention provides a preparation method of carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material, which comprises the following steps of stirring and mixing carbazolyl-containing metalloporphyrin and carbazolyl-containing quaternary phosphonium salt monomer in an inert atmosphere in the presence of an oxidant and an organic solvent, and carrying out oxidation reaction to obtain the polycarbozolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material, wherein the preparation method comprises the following steps:
(1) preparing metal porphyrin containing carbazolyl and quaternary phosphonium salt monomer containing carbazolyl;
(2) dissolving an organic solvent in a mixed solution of metal porphyrin containing carbazolyl and quaternary phosphonium salt monomer containing carbazolyl to support component A, and simultaneously mixing an oxidant and the organic solvent to form component B;
(3) dripping the component A prepared in the step (2) into the component B, stirring under an inert atmosphere to perform oxidation reaction, adding methanol, continuing stirring for 1h after the reaction is stopped, and performing suction filtration to obtain a solid filter cake after the stirring is finished;
(4) and washing the solid filter cake with methanol, dichloromethane and tetrahydrofuran in sequence, purifying the solid filter cake by a Soxhlet extraction method, and washing with methanol and tetrahydrofuran again to finally obtain the quaternary phosphonium salt containing the polycarbazolyl and the metalloporphyrin polymer microporous material.
Preferably, the oxidant is one of ferric trichloride, potassium permanganate, ammonium ceric nitrate, potassium persulfate, ammonium persulfate and hydrogen peroxide.
Preferably, the organic solvent is one of dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, acetone, acetonitrile, dioxane, benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene and trichlorobenzene.
Preferably, the molar ratio of the metal porphyrin containing carbazolyl to the quaternary phosphonium salt monomer containing carbazolyl is 1 (2-3); the molar ratio of the mixture of the metal porphyrin containing the carbazolyl group and the quaternary phosphonium salt monomer containing the carbazolyl group to the oxidant is 1 (10-20).
Preferably, the temperature of the oxidation reaction is between normal temperature and 15 ℃, and the reaction time is 12 to 36 hours.
Preferably, the metalloporphyrin is zinc porphyrin.
Preferably, the preparation method of the carbazolyl-containing zinc porphyrin comprises the following steps: dissolving porphyrin in dimethylformamide, dissolving zinc acetate in methanol, mixing and stirring the solution at 110-120 ℃ for reaction for 4-5 h, cooling to room temperature after the reaction is finished, pouring into ice water, filtering to obtain a crude product, and purifying the crude product by silica gel column chromatography to obtain the carbazolyl-containing zinc porphyrin.
Preferably, the preparation method of the carbazolyl-containing quaternary phosphonium salt monomer comprises the following steps: placing p-carbazole phenoxy bromopropane and triphenylphosphine into a flask filled with tetrahydrofuran, stirring and reacting for 20-24 h under the condition of oil bath at 100-110 ℃, cooling after complete reaction, removing a solvent under the condition of reduced pressure, and purifying by silica gel column chromatography to obtain the carbazolyl-containing quaternary phosphonium salt monomer.
The invention provides a carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material, which is prepared by the preparation method and has the following structure:
the invention also provides application of the carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material in the aspects of gas adsorption and conversion detection and heterogeneous catalysis.
The invention has the following beneficial effects:
1. the carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material mainly takes porphyrin as a framework, has a firm structure, can control the combination of various metal ions and porphyrin, has good catalytic activity and carbon dioxide fixing capacity, further improves the catalytic performance of zinc porphyrin after the zinc porphyrin and the quaternary phosphonium salt are subjected to oxidation reaction, and simultaneously forms an organic porous material with good adsorption performance, wherein the pore size of the organic porous material is 0.68-2.0 nm, and the specific surface area of the organic porous material is 342-369 cm2The catalyst has good adsorption effect on carbon dioxide, can be applied to aspects of carbon dioxide storage, molecular isolation and the like, and has the characteristics of convenient recovery, reutilization and good heat resistance as a catalyst.
2. The carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material prepared by the invention is a bifunctional catalyst and can be applied to the reaction of catalyzing carbon dioxide and epoxy compound to generate cyclic carbonate, and x is carried in the carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material-Anion, can freely supply epoxide at a proper angle, so the material does not need to strictly adjust the length of the carbon chain when being used as a bifunctional catalyst; meanwhile, a catalytic unit of the quaternary phosphonium salt in the carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material is connected to the meta position of the carbazole ring to ensure the coordination space of the epoxide, and a metal center and Br anions can be respectively used as Lewis acid and a nucleophilic reagent to cooperatively open the epoxide ring and convert the epoxide into the cyclic carbonate.
Drawings
FIG. 1 is a nitrogen absorption-desorption isotherm graph of microporous materials containing carbazolyl-containing quaternary phosphonium salts and metalloporphyrin polymers prepared in examples 1 and 2 according to the present invention;
FIG. 2 is a pore size distribution diagram of a carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material prepared according to example 1 and example 2 of the present invention;
FIG. 3 is a solid NMR carbon spectrum of a carbazole-based quaternary phosphonium salt-containing microporous material and a metalloporphyrin polymer microporous material prepared in example 1 and example 2 according to the present invention;
FIG. 4 is a thermogravimetric analysis curve of the carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous materials prepared in examples 1 and 2 according to the present invention;
FIG. 5 is a carbon dioxide absorption curve of a carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material prepared according to examples 1 and 2 of the present invention;
FIG. 6 is an XPS spectrum of a quaternary phosphonium salt and metalloporphyrin polymer microporous material containing carbazolyl groups prepared according to example 1 of the present invention.
Detailed Description
The invention will be further described with reference to preferred embodiments.
Example 1
A preparation method of carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material comprises the following steps of stirring and mixing carbazolyl-containing metalloporphyrin and carbazolyl-containing quaternary phosphonium salt monomer under the condition that ferric trichloride is used as an oxidant and dichloromethane is used as an organic solvent in an inert atmosphere, and carrying out oxidation reaction to obtain the polycarbozolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material, wherein the preparation method comprises the following specific steps:
(1) preparing metal porphyrin containing carbazolyl and quaternary phosphonium salt monomer containing carbazolyl;
(2) dissolving 15mL of anhydrous dichloromethane into a mixed solution of 0.1mmol of metal porphyrin containing carbazolyl and 0.2mmol of quaternary phosphonium salt monomer containing carbazolyl to prepare a component A, wherein the molar ratio of the metal porphyrin containing carbazolyl to the quaternary phosphonium salt monomer containing carbazolyl in the component A is 1:2, and simultaneously mixing 6.0mmol of ferric trichloride with 25mL of anhydrous dichloromethane to form a component B;
(3) dropping the component A prepared in the step (2) into the component B, wherein the molar ratio of the mixture of the metal porphyrin containing the carbazolyl group, the quaternary phosphonium salt monomer containing the carbazolyl group and the ferric chloride oxidant in the mixed solution is 3:20, stirring at normal temperature for 24 hours in an inert atmosphere, adding 50mL of methanol after reaction, continuing stirring for 1 hour after the reaction is stopped, and performing suction filtration after the stirring to obtain a solid filter cake;
(4) washing the solid filter cake with methanol, dichloromethane and tetrahydrofuran in sequence, purifying the solid filter cake by a Soxhlet extraction method, washing with methanol and tetrahydrofuran again, and finally obtaining the carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material CPBr-1.
Preferably, the metalloporphyrin is zinc porphyrin.
Preferably, the preparation method of the carbazolyl-containing zinc porphyrin comprises the following steps: dissolving 0.075mmol of porphyrin in 75mL of dimethylformamide, dissolving 0.15mmol of zinc acetate in 20mL of methanol, mixing and stirring the solution for reaction at 120 ℃, cooling to room temperature after the reaction is finished, pouring into ice water, filtering to obtain a crude product, and purifying the crude product by silica gel column chromatography to obtain the carbazolyl-containing zinc porphyrin.
Preferably, the preparation method of the carbazolyl-containing quaternary phosphonium salt monomer is as follows: putting 0.788mmol of p-carbazole phenoxy bromopropane and 1.183mmol of triphenylphosphine into a 50mL flask filled with 15mL of tetrahydrofuran, stirring and reacting for 24h under the condition of 100 ℃ oil bath, cooling after complete reaction, removing the solvent under the condition of reduced pressure, and purifying by silica gel column chromatography to obtain the carbazolyl-containing quaternary phosphonium salt monomer.
Example 2
A preparation method of carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material comprises the following steps of stirring and mixing carbazolyl-containing metalloporphyrin and carbazolyl-containing quaternary phosphonium salt monomer under the condition that ferric trichloride is used as an oxidant and dichloromethane is used as an organic solvent in an inert atmosphere, and carrying out oxidation reaction to obtain the polycarbozolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material, wherein the preparation method comprises the following specific steps:
(1) preparing metal porphyrin containing carbazolyl and quaternary phosphonium salt monomer containing carbazolyl;
(2) dissolving 15mL of anhydrous dichloromethane into a mixed solution of 0.1mmol of metal porphyrin containing carbazolyl and 0.3mmol of quaternary phosphonium salt monomer containing carbazolyl to prepare a component A, wherein the molar ratio of the metal porphyrin containing carbazolyl to the quaternary phosphonium salt monomer containing carbazolyl in the component A is 1:3, and simultaneously mixing 4.0mmol of ferric trichloride with 25mL of anhydrous dichloromethane to form a component B;
(3) dropping the component A prepared in the step (2) into the component B, wherein the molar ratio of the mixture of the metal porphyrin containing the carbazolyl, the quaternary phosphonium salt monomer containing the carbazolyl and the ferric chloride oxidant in the mixed solution is 1:10, stirring at 150 ℃ for 12h under an inert atmosphere, adding 50mL of methanol after reaction is stopped, continuing stirring for 1h, and performing suction filtration after stirring to obtain a solid filter cake;
(4) and washing the solid filter cake with methanol, dichloromethane and tetrahydrofuran in sequence, purifying the solid filter cake by a Soxhlet extraction method, washing with methanol and tetrahydrofuran again, and finally obtaining the carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material CPBr-2.
Preferably, the metalloporphyrin is zinc porphyrin.
Preferably, the preparation method of the carbazolyl-containing zinc porphyrin comprises the following steps: dissolving 0.075mmol of porphyrin in 75mL of dimethylformamide, dissolving 0.15mmol of zinc acetate in 20mL of methanol, mixing and stirring the solution for reaction at 110 ℃ for 5 hours, cooling to room temperature after the reaction is finished, pouring into ice water, filtering to obtain a crude product, and purifying the crude product by silica gel column chromatography to obtain the carbazolyl-containing zinc porphyrin.
Preferably, the preparation method of the carbazolyl-containing quaternary phosphonium salt monomer comprises the following steps of placing 0.788mmol of p-carbazole phenoxybromopropane and 1.183mmol of triphenylphosphine in a 50mL flask containing 15mL of tetrahydrofuran, stirring and reacting for 20h under the condition of 110 ℃ oil bath, cooling after complete reaction, removing the solvent under the condition of reduced pressure, and purifying by silica gel column chromatography to obtain the carbazolyl-containing quaternary phosphonium salt monomer.
In the above examples 1 and 2, the chemical reaction formulas of the carbazolyl-containing quaternary phosphonium salt and the metalloporphyrin polymer microporous material are as follows:
wherein Zn-TCPP is zinc porphyrin containing carbazolyl, CZPBR is quaternary phosphonium salt monomer containing carbazolyl, and CPBr is quaternary phosphonium salt containing carbazolyl and metalloporphyrin polymer microporous material.
In the above examples 1 and 2, the chemical reaction formula of the carbazolyl-containing zinc porphyrin is as follows:
wherein TCPP is porphyrin, and Zn-TCPP is zinc porphyrin containing carbazolyl.
Performing mass spectrometry on the carbazolyl-containing zinc porphyrin by using a liquid chromatography-mass spectrometry (LC-MS), wherein a mass spectrometry spectrogram shows that a characteristic peak appears at 562.22m/z and accords with the relative molecular mass of the carbazolyl-containing zinc porphyrin; performing solid nuclear magnetic resonance detection on the carbazolyl-containing zinc porphyrin by using a nuclear magnetic resonance spectrometer (BRUKER AVANCE III 400), wherein the nuclear magnetic resonance carbon spectrum shows that the hybridization types of carbon atoms are all sp2And meets the structural characteristics of the zinc porphyrin containing carbazolyl.
In the above examples 1 and 2, the formula of the carbazolyl-containing quaternary phosphonium salt monomer is as follows:
wherein, PPh3Is triphenylphosphine and CZPBR is a quaternary phosphonium salt monomer containing carbazolyl.
Performing mass spectrometry on the carbazolyl-containing quaternary phosphonium salt monomer by using a liquid chromatography-mass spectrometry (LC-MS), wherein a mass spectrometry spectrum shows that a characteristic peak appears at 562.22m/z and the characteristic peak accords with the relative molecular mass of the carbazolyl organic porous polymer; performing solid nuclear magnetic resonance detection on the carbazolyl-containing quaternary phosphonium salt monomer by using a nuclear magnetic resonance spectrometer (BRUKER AVANCE III 400), wherein the nuclear magnetic resonance carbon spectrum shows that the hybridization types of carbon atoms are all sp2Meets the structural characteristics of the carbazolyl-containing quaternary phosphonium salt monomer.
Example 3
And (3) testing the catalytic performance of the carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material:
the catalytic performance of the CPBr-1 prepared in example 1 and the CPBr-2 prepared in example 2 was tested, different substituted epoxypropanes were used as model compounds, no additional solvent was added under the reaction conditions of 2.5MPa and 90 ℃, the cyclic carbonates were prepared by the addition reaction of carbon dioxide and epoxide ring with CPBr-1 and CPBr-2 as catalysts, respectively, and the specific chemical reaction formula is as follows:
in the case of two low yield monomers using no catalyst and a synthesis catalyst, almost no cyclic carbonate product was detected, and the yields of cyclic carbonate were 84% and 91% with CPBr-1 and CPBr-2 as catalysts, respectively.
Performance test analysis of carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material:
referring to fig. 1, the nitrogen adsorption-desorption isotherm curves of CPBr-1 and CPBr-2 prepared according to examples 1 and 2 of the present invention are a combination of type i and type iv (classification of BDDT), and the isotherm shows a high adsorption amount at a low relative pressure, indicating the presence of micropores (type i), and the curves show a hysteresis loop in a relative pressure range of 0.4 to 1, indicating the presence of mesoporous distribution.
Referring to FIG. 2, the BET specific surface area was 342m when the specific surface area and porosity of solid CPBr-1 and CPBr-2 were measured by a full-automatic specific surface area and porosity analyzer (Micromeritics ASAP 2460)2(ii)/g and 369m2The pore diameters of CPBr-1 and CPBr-2 calculated by the theory of non-localized density functional are mainly distributed at 0.68nm and 0.71 nm.
Referring to FIG. 3, CPBr-1 and CPBr-2 prepared according to examples 1 and 2 of the present invention were characterized at the molecular level by solid state 13C CP/MAS NMR spectra, where the signal resonances associated with macrocyclic porphyrins and carbazolyl benzenes were consistent with the reported data, the resonances around 60ppm could be attributed to aliphatic carbon atoms, possibly including quaternary ammonium salts and alkoxy carbon atoms, and the carbon resonance on the alkoxy could overlap with the last carbon on the alkyl chain. Possibly including both the quaternary carbon and alkoxy carbon atoms, the spectrum gave a signal at 19.4ppm with chemical shifts similar to those observed for the quaternary phosphonium salt monomer, indicating that the quaternary ammonium structure was preserved.
Referring to fig. 4, thermogravimetric analysis was performed on CPBr-1 and CPBr-2 prepared according to examples 1 and 2 of the present invention, the polymer loss mass was 4% at 300 ℃, the weight loss below 120 ℃ was generally attributed to the evaporation of water and gas molecules adsorbed in the micropores, the polymer network structure continued to decompose around 300 ℃, the residual mass varied from 78% to 55%, the thermal stability of the sample CPBr-1 was slightly greater than CPBr-2 from the weight loss rate, the thermal stability of CPBr-1 could be improved due to the interaction between Zn and the porphyrin ring, and the sample decomposition amount in the final product was relatively low. The thermal stability of the carbazolyl-containing quaternary phosphonium salt and the metalloporphyrin polymer is further determined, and the thermal stability is especially important in carbon dioxide catalytic reaction.
Referring to FIG. 5, in order to obtain carbon dioxide adsorption curves of CPBr-1 and CPBr-2 as catalysts by using a physical adsorption apparatus (Micromeritics Tristar 3020), it was found that the carbon dioxide capturing capacities (1bar/273k) of CPBr-1 and CPBr-2 were 5.76% and 8.81%, respectively.
Referring to FIG. 6, the X-ray photoelectron spectroscopy analysis of CPBr-1 obtained in example 1 of the present invention revealed that the binding energy of P2P was 130.4 eV. The binding energy of Br 3d is 69eV, and O1 s and N1s also appear at 401eV and 532eV respectively, so that X-ray photoelectron spectroscopy tests further confirm the successful synthesis of metalloporphyrin and quaternary ammonium salt polymers.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, so that any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention without departing from the content of the technical solution of the present invention.
Claims (5)
1. A preparation method of carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material is characterized in that: the carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material has the following structure:
in an inert atmosphere, under the condition that an oxidant and an organic solvent exist, metal porphyrin containing carbazolyl and a quaternary phosphonium salt monomer containing carbazolyl are stirred and mixed, and after an oxidation reaction, the quaternary phosphonium salt containing the polycarbazolyl and the metal porphyrin polymer microporous material are obtained, and the method specifically comprises the following steps:
(1) preparing metal porphyrin containing carbazolyl and quaternary phosphonium salt monomer containing carbazolyl, wherein the metal porphyrin is zinc porphyrin;
(2) dissolving an organic solvent in a mixed solution of metal porphyrin containing carbazolyl and quaternary phosphonium salt monomer containing carbazolyl to support component A, and simultaneously mixing an oxidant and the organic solvent to form component B;
(3) dripping the component A prepared in the step (2) into the component B, stirring under an inert atmosphere to perform oxidation reaction, adding methanol, continuing stirring for 1h after the reaction is stopped, and performing suction filtration to obtain a solid filter cake after the stirring is finished;
(4) washing the solid filter cake with methanol, dichloromethane and tetrahydrofuran in sequence, purifying the solid filter cake by a Soxhlet extraction method, washing with methanol and tetrahydrofuran again, and finally obtaining the carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material;
the preparation method of the carbazolyl-containing zinc porphyrin comprises the following steps: dissolving porphyrin containing carbazolyl in dimethylformamide, dissolving zinc acetate in methanol, mixing and stirring the solution at 110-120 ℃ for reaction for 4-5 h, cooling to room temperature after the reaction is finished, pouring into ice water, filtering to obtain a crude product, and purifying the crude product by silica gel column chromatography to obtain zinc porphyrin containing carbazolyl;
the preparation method of the carbazolyl-containing quaternary phosphonium salt monomer comprises the following steps: placing p-carbazole phenoxy bromopropane and triphenylphosphine into a flask filled with tetrahydrofuran, stirring and reacting for 20-24 h under the condition of oil bath at 100-110 ℃, cooling after complete reaction, removing a solvent under the condition of reduced pressure, and purifying by silica gel column chromatography to obtain the carbazolyl-containing quaternary phosphonium salt monomer.
2. The method for preparing the carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material according to claim 1, wherein: the oxidant is one of ferric trichloride, potassium permanganate, ammonium ceric nitrate, potassium persulfate, ammonium persulfate and hydrogen peroxide.
3. The method for preparing a carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material according to claim 1, wherein: the organic solvent is one of dichloromethane, trichloromethane, carbon tetrachloride, tetrahydrofuran, acetone, acetonitrile, dioxane, benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene and trichlorobenzene.
4. The method for preparing a carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material according to claim 1, wherein: the molar ratio of the metal porphyrin containing the carbazolyl to the quaternary phosphonium salt monomer containing the carbazolyl is 1 (2-3); the molar ratio of the mixture of the metal porphyrin containing the carbazolyl group and the quaternary phosphonium salt monomer containing the carbazolyl group to the oxidant is 1 (10-20).
5. The method for preparing a carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material according to claim 1, wherein: the temperature of the oxidation reaction is normal temperature-15 ℃, and the reaction time is 12-36 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910993619.XA CN110655642B (en) | 2019-10-18 | 2019-10-18 | Carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910993619.XA CN110655642B (en) | 2019-10-18 | 2019-10-18 | Carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110655642A CN110655642A (en) | 2020-01-07 |
| CN110655642B true CN110655642B (en) | 2022-07-08 |
Family
ID=69041193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910993619.XA Expired - Fee Related CN110655642B (en) | 2019-10-18 | 2019-10-18 | Carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110655642B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116920948B (en) * | 2023-09-15 | 2023-12-29 | 山东海化集团有限公司 | Metalloporphyrin-based bifunctional catalyst and preparation method and application thereof |
| CN117088390B (en) * | 2023-10-19 | 2024-02-09 | 深圳新宙邦科技股份有限公司 | Preparation method of hexafluorophosphate, electrolyte and secondary battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4012957A1 (en) * | 1990-04-24 | 1991-10-31 | Bayer Ag | Colourless block copolymer(s) prodn. - by polymerisation of alkylene oxide(s) and cyclic carbonate(s) in presence of aluminium porphyrin initiator |
| WO2016054798A1 (en) * | 2014-10-10 | 2016-04-14 | 中国科学院长春应用化学研究所 | Preparation method for cyclic carbonate |
| CN108440488A (en) * | 2017-02-16 | 2018-08-24 | 中国科学院大连化学物理研究所 | A kind of Porous-Organic copolymer multifunctional bionic heterogeneous catalyst and preparation method thereof |
-
2019
- 2019-10-18 CN CN201910993619.XA patent/CN110655642B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4012957A1 (en) * | 1990-04-24 | 1991-10-31 | Bayer Ag | Colourless block copolymer(s) prodn. - by polymerisation of alkylene oxide(s) and cyclic carbonate(s) in presence of aluminium porphyrin initiator |
| WO2016054798A1 (en) * | 2014-10-10 | 2016-04-14 | 中国科学院长春应用化学研究所 | Preparation method for cyclic carbonate |
| CN108440488A (en) * | 2017-02-16 | 2018-08-24 | 中国科学院大连化学物理研究所 | A kind of Porous-Organic copolymer multifunctional bionic heterogeneous catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "有机多孔聚咔唑的制备及性能研究进展";操强等;《化学学报》;20151231;第541-556页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110655642A (en) | 2020-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qian et al. | Imine and imine-derived linkages in two-dimensional covalent organic frameworks | |
| Du et al. | Construction of a PPIL@ COF core–shell composite with enhanced catalytic activity for CO 2 conversion | |
| Zhao et al. | Design and synthesis of novel pyridine-rich cationic covalent triazine framework for CO2 capture and conversion | |
| KR101474579B1 (en) | Synthesis, characterization and design of crystalline 3d- and 2d-covalent organic frameworks | |
| Yuan et al. | Pyridyl ionic liquid functionalized ZIF-90 for catalytic conversion of CO 2 into cyclic carbonates | |
| Modak et al. | A triazine functionalized porous organic polymer: excellent CO 2 storage material and support for designing Pd nanocatalyst for C–C cross-coupling reactions | |
| US8298986B2 (en) | Structures for capturing CO2, methods of making the structures, and methods of capturing CO2 | |
| CN107814946B (en) | Cationic covalent organic framework compound and preparation method thereof | |
| Xu et al. | N, N′-Bicarbazole-based covalent triazine frameworks as high-performance heterogeneous photocatalysts | |
| CN110655642B (en) | Carbazolyl-containing quaternary phosphonium salt and metalloporphyrin polymer microporous material as well as preparation method and application thereof | |
| CN107428917A (en) | The modified porous super cross-linked polymer for capturing and converting for CO2 | |
| Zhang et al. | Robust cationic calix [4] arene polymer as an efficient catalyst for cycloaddition of epoxides with CO2 | |
| Lu et al. | Porous organic polymers containing zinc porphyrin and phosphonium bromide as bifunctional catalysts for conversion of carbon dioxide | |
| CN106378109B (en) | A kind of porous polycarbazole polymer and its preparation method and application | |
| CN105120983A (en) | Ionic liquid grafted mesoporous silica compositions for polar gas/non-polar gas and olefin/paraffin separations | |
| Kim et al. | Transition metal complex directed synthesis of porous cationic polymers for efficient CO2 capture and conversion | |
| CN113683740A (en) | Halogen ion functionalized organic porous material and preparation method and application thereof | |
| Leo et al. | A double basic Sr-amino containing MOF as a highly stable heterogeneous catalyst | |
| Zhang et al. | Covalent organic frameworks embedding single cadmium sites for efficient carboxylative cyclization of CO 2 with propargylic amines | |
| Zang et al. | Synthesis of Pd/conjugated microporous polymer heterogeneous catalysts via imine groups and high catalytic efficiency on Suzuki–Miyaura coupling reaction | |
| CN111269417A (en) | Pyridyl-containing conjugated microporous polymer and preparation method and application thereof | |
| CN111732736B (en) | Ni (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof | |
| Wei et al. | A benzimidazole‐linked porphyrin covalent organic polymers as efficient heterogeneous catalyst/photocatalyst | |
| CN109762142B (en) | Conjugated polymer material for regulating and controlling carbon dioxide adsorption based on photothermal effect | |
| CN108940361B (en) | Chiral ionic porous organic polymer material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220708 |